Gas cabinet assembly comprising sorbent-based gas storage and delivery system

ABSTRACT

A gas supply system including a gas cabinet defining an enclosure including therein a gas dispensing manifold and one or more adsorbent-based gas storage and dispensing vessels mounted in the enclosure and joined in gas flow communication with the gas dispensing manifold. The enclosure may be maintained under low or negative pressure conditions for enhanced safety in the event of leakage of gas from the gas storage and dispensing vessel(s) in the enclosure. The gas supply system may be coupled to a gas-consuming unit in a semiconductor manufacturing facility, e.g., an ion implanter, an etch chamber, or a chemical vapor deposition reactor.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a continuation-in-part of U.S. patent application Ser. No.09/082,596, filed on May 21, 1998, now U.S. Pat. No. 6,132,492, which isa continuation-in-part of Ser. No. 08/809,019 filed Mar. 27, 1998 nowU.S. Pat. No. 5,935,305 in the United States Patent and Trademark Officeas a Designated/Elected Office (DO/EO/US) under the provisions of 35 USC371, based on PCT international application no. PCT/US95/13040 filed onOct. 13, 1995 designating the United States as a Designated State, andclaiming the priority of U.S. patent application Ser. No. 08/322,224filed Oct. 13, 1994 and issued May 21, 1996 as U.S. Pat. No. 5,518,528.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates generally to storage and dispensing systems forthe selective dispensing of gaseous reagents, e.g., hydride and halidegases, from a vessel or storage container in which the gas component(s)are held in sorptive relationship to a solid sorbent medium, and aredesorptively released from the sorbent medium in the dispensingoperation. The invention relates more specifically to gas cabinetassemblies containing one or more sorbent-based gas storage anddispensing vessels of such type, coupled to a gas dispensing manifoldand/or other flow circuitry, to selectively dispense the gas from thevessel and gas cabinet to a downstream process unit, e.g., asemiconductor manufacturing facility.

2. Description of the Related Art

In the manufacture of semiconductor materials and devices, and invarious other industrial processes and applications, there is a need fora reliable source of hydridic and halidic gases. Many of such gases,including for example silane, germane, ammonia, phosphine, arsine,diborane, stibine, hydrogen sulfide, hydrogen selenide, hydrogentelluride, and corresponding and other halide (chlorine, bromine,iodine, and fluorine) compounds, as a result of toxicity and safetyconsiderations, must be carefully stored and handled in the industrialprocess facility.

The gaseous hydrides arsine (AsH₃) and phosphine (PH₃) are commonly usedas sources of arsenic (As) and phosphorous (P) in ion implantation. Dueto their extreme toxicity and high vapor pressure, their use,transportation and storage raise significant safety concerns for thesemiconductor industry. Ion implantation systems typically use dilutemixtures of AsH₃ and PH₃ at pressures as high as 1500 psig. Acatastrophic release of these high pressure cylinders could pose aserious injury potential and even death to fab workers.

Based on these considerations, the ion implant user must choose betweensolid or gas sources for arsenic and phosphorous species. Switching fromAs to P on an implanter with solid sources can take as long as 90minutes. The same species change requires only 15 minutes with gassources. However, arsine (AsH₃) and phosphine (PH₃), the two mostcommonly used source gases, are highly toxic. Their use has recentlybeen the focus of widespread attention due to the safety aspects ofhandling and processing these gases. Many ion implantation systemsutilize hydride gas sources supplied as dilute mixtures (10-15%), ineither 0.44 L or 2.3 L cylinders at pressures of 400-1800 psig. It isthe concern over the pressure-driven release of the gases from cylindersthat has prompted users to investigate safer alternatives.

U.S. Pat. No. 4,744,221 issued May 17, 1988 to Karl O. Knollmuellerdiscloses a method of storing and subsequently delivering arsine, bycontacting arsine at a temperature of from about −30° C. to about +30°C. with a zeolite of pore size in the range of from about 5 to about 15Angstroms to adsorb arsine on the zeolite, and then dispensing thearsine by heating the zeolite to an elevated temperature of up to about175° C. for sufficient time to release the arsine from the zeolitematerial.

The method disclosed in the Knollmueller patent is disadvantageous inthat it requires the provision of heating means for the zeolitematerial, which must be constructed and arranged to heat the zeolite tosufficient temperature to desorb the previously sorbed arsine from thezeolite in the desired quantity.

The use of a heating jacket or other means exterior to the vesselholding the arsine-bearing zeolite is problematic in that the vesseltypically has a significant heat capacity, and therefore introduces asignificant lag time to the dispensing operation. Further, heating ofarsine causes it to decompose, resulting in the formation of hydrogengas, which introduces an explosive hazard into the process system.Additionally, such thermally-mediated decomposition of arsine effectssubstantial increase in gas pressure in the process system, which may beextremely disadvantageous from the standpoint of system life andoperating efficiency.

The provision of interiorly disposed heating coil or other heatingelements in the zeolite bed itself is problematic since it is difficultwith such means to uniformly heat the zeolite bed to achieve the desireduniformity of arsine gas release.

The use of heated carrier gas streams passed through the bed of zeolitein its containment vessel may overcome the foregoing deficiencies, butthe temperatures necessary to achieve the heated carrier gas desorptionof arsine may be undesirably high or otherwise unsuitable for the enduse of the arsine gas, so that cooling or other treatment is required tocondition the dispensed gas for ultimate use.

The present invention contemplates a gas storage and dispensing system,for the storage and dispensing of reagent gases, such as hydride andhalide gases, which overcomes the above-discussed disadvantages of themethod disclosed in the Knollmueller patent.

The system of the invention is adapted for storage and dispensing of awide variety of reagent gases, including hydride and halide gases, andis selectively operable at ambient temperature levels, but is able toeffectively utilize the high storage (sorptive) capacity of physicaladsorbents such as zeolite materials.

SUMMARY OF THE INVENTION

The present invention relates to a gas supply system. The gas supplysystem includes a gas cabinet defining an enclosure including therein agas dispensing manifold and one or more adsorbent-based gas storage anddispensing vessels mounted in the enclosure and joined in gas flowcommunication with the gas dispensing manifold.

The enclosure may be maintained under low or negative pressureconditions for enhanced safety in the event of leakage of gas from thegas storage and dispensing vessel(s) in the enclosure. The gas supplysystem may be coupled to a downstream gas-consuming unit, such as aprocess unit in a semiconductor manufacturing facility, e.g., an ionimplanter, an etch chamber, a chemical vapor deposition reactor, etc.

The adsorbent-based gas storage and dispensing system constitutes anadsorption-desorption apparatus for storage and dispensing of a gas,e.g., a gas selected from the group consisting of hydride gases, halidegases, and organometallic reagent gases, such as Group V compounds. Theadsorption-desorption apparatus comprises:

a storage and dispensing vessel constructed and arranged for holding asolid-phase physical sorbent medium, and for selectively flowing gasinto and out of the vessel;

a solid-phase physical sorbent medium disposed in said storage anddispensing vessel at an interior gas pressure;

a sorbate gas physically adsorbed on said solid-phase physical sorbentmedium;

a dispensing assembly coupled in gas flow communication with the storageand dispensing vessel, and constructed and arranged to provide,exteriorly of said storage and dispensing vessel, a pressure below saidinterior pressure, to effect desorption of sorbate gas from thesolid-phase physical sorbent medium, and gas flow of desorbed gasthrough the dispensing assembly;

wherein the solid-phase physical sorbent medium is devoid of tracecomponents selected from the group consisting of water, metals, andoxidic transition metal species (e.g., oxides, sulfites and/or nitrates)sufficient in concentration to decompose the sorbate gas in said storageand dispensing vessel.

In such apparatus, the solid-phase physical sorbent medium contains lessthan 350, preferably less than 100, more preferably less than 10, andmost preferably less than 1, parts-per-million by weight of tracecomponents selected from the group consisting of water and oxidictransition metal species, based on the weight of the physical sorbentmedium.

In the apparatus of the invention, the solid-phase physical sorbentmedium concentration of trace components selected from the groupconsisting of water and oxidic transition metal species, based on theweight of the physical sorbent medium, desirably is insufficient todecompose more than 5%, and preferably more than 1% by weight of thesorbate gas after 1 year at 25° C. and said interior pressure.

In another aspect, the present invention relates to anadsorption-desorption apparatus, for storage and dispensing of a gas,e.g., a gas selected from the group consisting of hydride gases, halidegases, and organometallic Group V compounds, said apparatus comprising:

a storage and dispensing vessel constructed and arranged for holding asolid-phase physical sorbent medium, and for selectively flowing gasinto and out of said vessel;

a solid-phase physical sorbent medium disposed in said storage anddispensing vessel at an interior gas pressure;

a sorbate gas physically adsorbed on said solid-phase physical sorbentmedium;

a dispensing assembly coupled in gas flow communication with the storageand dispensing vessel, and constructed and arranged to provide,exteriorly of said storage and dispensing vessel, a pressure below saidinterior pressure, to effect desorption of sorbate gas from thesolid-phase physical sorbent medium, and gas flow of desorbed gasthrough the dispensing assembly;

wherein the solid-phase physical sorbent medium concentration of tracecomponents selected from the group consisting of water, metals, andoxidic transition metal species, based on the weight of the physicalsorbent medium, is insufficient to cause decomposition of the sorbategas resulting in more than a 25%, and preferably more than a 10% rise ininterior pressure after 1 week at 25° C. in said storage and dispensingvessel.

In such apparatus, the solid-phase physical sorbent medium desirablycontains less than 350, preferably less than 100, more preferably lessthan 10, and most preferably less than 1, part(s)-per-million by weightof trace components selected from the group consisting of water andoxidic transition metal species, based on the weight of the physicalsorbent medium.

Still another aspect of the invention relates to anadsorption-desorption apparatus, for storage and dispensing of borontrifluoride, such apparatus comprising:

a storage and dispensing vessel constructed and arranged for holding asolid-phase physical sorbent medium having a sorptive affinity for borontrifluoride, and for selectively flowing boron trifluoride into and outof said vessel;

a solid-phase physical sorbent medium having a sorptive affinity forboron trifluoride, disposed in said storage and dispensing vessel at aninterior gas pressure;

boron trifluoride gas, physically adsorbed on said solid-phase physicalsorbent medium; and

a dispensing assembly coupled in gas flow communication with the storageand dispensing vessel, and constructed and arranged to provide,exteriorly of said storage and dispensing vessel, a pressure below saidinterior pressure, to effect desorption of boron trifluoride gas fromthe solid-phase physical sorbent medium, and gas flow of desorbed borontrifluoride gas through the dispensing assembly.

Although generally preferred to operate solely by pressure differential,in respect of the sorption and desorption of the gas to be subsequentlydispensed, the system of the invention may in some instancesadvantageously employ a heater operatively arranged in relation to thestorage and dispensing vessel for selective heating of the solid-phasephysical sorbent medium, to effect thermally-enhanced desorption of thesorbate gas from the solid-phase physical sorbent medium.

A preferred solid-phase physical sorbent medium comprises a crystallinealuminosilicate composition, e.g., with a pore size in the range of fromabout 4 to about 13 Å, although crystalline aluminosilicate compositionshaving larger pores, e.g., so-called mesopore compositions with a poresize in the range of from about 20 to about 40 Å are also potentiallyusefully employed in the broad practice of the invention. Examples ofsuch crystalline aluminosilicate compositions include 5 Å molecularsieve, and preferably a binderless molecular sieve. Although molecularsieve materials such as crystalline aluminosilicates and carbonmolecular sieves are preferred in many instances, the solid-phasephysical sorbent medium may usefully comprise other materials such assilica, alumina, macroreticulate polymers, kieselguhr, carbon, etc. Thesorbent materials may be suitably processed or treated to ensure thatthey are devoid of trace components which deleteriously affect theperformance of the gas storage and dispensing system. For example,carbon sorbents may be subjected to washing treatment, e.g., withhydrofluoric acid, to render them sufficiently free of trace componentssuch as metals and oxidic transition metal species. Potentially usefulcarbon materials include so-called bead activated carbon of highlyuniform spherical particle shape, e.g., BAC-MP, BAC-LP, and BAC-G-70R,available from Kureha Corporation of America, New York, N.Y.

The apparatus of the invention may be constructed with a solid-phasephysical sorbent medium being present in the storage and dispensingvessel together with a chemisorbent material having a sorptive affinityfor contaminants, e.g., decomposition products, of the sorbate gastherein. Such chemisorbent material may for example have a sorptiveaffinity for non-inert atmospheric gases. Examples of potentiallysuitable chemisorbent materials include a scavenger for suchcontaminants, such as a scavenger selected from the group consisting of:

(A) scavengers including a support having associated therewith, but notcovalently bonded thereto, a compound which in the presence of suchcontaminant provides an anion which is reactive to effect the removal ofsuch contaminant, said compound being selected from one or more membersof the group consisting of:

(i) carbanion source compounds whose corresponding protonated carbanioncompounds have a pKa value of from about 22 to about 36; and

(ii) anion source compounds formed by reaction of said carbanion sourcecompounds with the sorbate gas; and

(B) scavengers comprising:

(i) an inert support having a surface area in the range of from about 50to about 1000 square meters per gram, and thermally stable up to atleast about 250° C.; and

(ii) an active scavenging species, present on the support at aconcentration of from about 0.01 to about 1.0 moles per liter ofsupport, and formed by the deposition on the support of a Group IA metalselected from sodium, potassium, rubidium, and cesium and their mixturesand alloys and pyrolysis thereof on said support.

By way of an example, such chemisorbent material may advantageouslycomprise a scavenger component selected from the group consisting of:trityllithium and potassium arsenide.

In respect of such chemisorbent materials for contaminants of thesorbate gas to be dispensed, any of a wide variety of scavengers orchemisorbent materials may be employed, including scavenger compositionsof the types disclosed and claimed in U.S. Pat. No. 4,761,395 issuedAug. 2, 1988 to Glenn M. Tom, et al., and U.S. Pat. No. 5,385,686 issuedJan. 31, 1995 to Glenn M. Tom and James V. McManus, the disclosures ofwhich hereby are incorporated herein by reference.

The chemisorbent material when employed may be utilized as a separatebed in gas communication with the bed of physical adsorbent, oralternatively the chemisorbent may be dispersed randomly or selectivelythroughout a bed of physical adsorbent material in the storage anddispensing vessel.

The invention in another aspect relates to an ion implantation system,comprising a reagent source for reagent source material and an ionimplantation apparatus coupled in gas flow communication with suchreagent source, and wherein the reagent source is of a type describedhereinabove.

The present invention relates in still another aspect to a process forsupplying a gas reagent selected from the group consisting of hydridegases, halide gases, and organometallic Group V compounds, such processcomprising:

providing a storage and dispensing vessel containing a solid-phasephysical sorbent medium having a physically sorptive affinity for saidgas reagent;

physically sorptively loading on said solid-phase physical sorbentmedium a sorbate gas selected from the group consisting of hydride gasesand boron halide gases, to yield a sorbate gas-loaded physical sorbentmedium; and

desorbing sorbate gas from the sorbate gas-loaded physical sorbentmedium, by reduced pressure desorption, for dispensing thereof;

wherein the solid-phase physical sorbent medium is devoid of tracecomponents selected from the group consisting of water, metals andoxidic transition metal species in a sufficient concentration todecompose the sorbate gas in said storage and dispensing vessel.

In a further particular aspect, the invention relates to anadsorption-desorption process for storage and dispensing of borontrifluoride, comprising:

providing a storage and dispensing vessel containing a solid-phasephysical sorbent medium having a physically sorptive affinity for borontrifluoride;

physically sorptively loading boron trifluoride on said solid-phasephysical sorbent medium, to yield a boron trifluoride-loaded physicalsorbent medium; and

selectively desorbing boron trifluoride from the borontrifluoride-loaded physical sorbent medium, by reduced pressuredesorption, for dispensing thereof.

Another apparatus aspect of the present invention relates to anadsorption-desorption apparatus, for storage and dispensing of a gassorbable on a solid-phase physical sorbent medium, such apparatuscomprising:

a storage and dispensing vessel constructed and arranged for holding asolid-phase physical sorbent medium, and for selectively flowing gasinto and out of said vessel;

a solid-phase physical sorbent medium disposed in the storage anddispensing vessel at an interior gas pressure;

a sorbate gas physically adsorbed on the solid-phase physical sorbentmedium;

a dispensing assembly coupled in gas flow communication with the storageand dispensing vessel, and constructed and arranged to provide,exteriorly of the storage and dispensing vessel, a pressure below saidinterior pressure, to effect desorption of sorbate gas from thesolid-phase physical sorbent medium, and gas flow of desorbed gasthrough the dispensing assembly;

a cryopump coupled to the dispensing assembly for pressurizing thedesorbed gas and discharging the resultingly pressurized gas.

In a further process aspect, the present invention relates to a processfor storage and dispensing of a gas sorbable on a solid-phase physicalsorbent medium, such process comprising:

providing a storage and dispensing vessel holding a solid-phase physicalsorbent medium;

adsorbing such gas on the solid-phase physical sorbent medium;

establishing, exteriorly of the storage and dispensing vessel, apressure below the interior pressure, to effect desorption of sorbategas from the solid-phase physical sorbent medium, and flowing desorbedgas out of the storage and dispensing vessel;

cryopumping the desorbed gas from the storage and dispensing vessel to apredetermined pressure, wherein such predetermined pressure is higherthan the pressure of the desorbed gas flowed out of the storage anddispensing vessel.

In all of the foregoing aspects, the gas storage and dispensing vesselof the invention may be deployed in a gas cabinet equipped with a gasdispensing manifold and associated flow circuitry therein, fordispensing of the gas desorbed from the sorbent material in the vesseland flowing the desorbed gas through the manifold flow circuitry and outof the cabinet to the gas-consumption unit. The gas storage anddispensing vessel and gas dispensing manifold may be associated with apump, fan, blower, turbine, eductor, ejector, compressor, cryopump, orother motive flow means, to provide the pressure drop and extraction ofthe gas from the sorbent material in the vessel, for flow into the gasdispensing manifold.

Another aspect of the invention relates to a semiconductor manufacturingsystem, comprising a gas cabinet of the foregoing type, coupled to asemiconductor manufacturing process unit.

Other aspects, features and embodiments of the invention will be morefully apparent from the ensuing disclosure and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a graph of the adsorption isotherm for arsine, as a plot ofthe arsine loading in grams arsine per liter of zeolite 5A, as afunction of the log pressure in Torr.

FIG. 2 shows a graph of the adsorption isotherm for arsine, as a plot ofthe arsine loading in grams phosphine per liter of zeolite 5A, as afunction of the log pressure in Torr.

FIG. 3 is a schematic representation of a storage and delivery systemaccording to one embodiment of the invention.

FIG. 4 is a delivery lifetime plot of arsine pressure, in Torr, as afunction of hours of operation of the storage and delivery systemapparatus.

FIG. 5 is a plot of cylinder pressure, in Torr, as a function of time,in seconds, as well as a plot (on the right-hand y-axis) of temperature,in degrees Centigrade, as a function of time, in seconds, graphicallyshowing the temperature and pressure rises during the experimentalbackfilling of a phosphine gas storage and delivery system apparatus,with room air.

FIG. 6 is a plot of arsine released, in grams, as a function of time, inseconds, for a standard cylinder of arsine, versus an arsine storage anddelivery system apparatus, in simulation of a worst case emissionincident.

FIG. 7 is a schematic perspective view of a cryopumping storage anddelivery system apparatus according to a further embodiment of theinvention.

FIG. 8 is a graph of storage and delivery system cylinder pressurelevel, in psia, as a function of elaspsed time, in minutes, for twomolecular sieve sorbent materials of differing iron content.

FIG. 9 is a frontal perspective view of a gas cabinet assemblyincorporating a sorbent-based gas storage and dispensing assemblyaccording to one embodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS THEREOF

The disclosures of the following patent applications and patents arehereby incorporated herein by reference in their entireties:

U.S. Pat. No. 5,935,305 issued Aug. 10, 1999;

PCT international application no. PCT/US95/13040 filed October 13,1995];

U.S. Pat. No. 5,518,528 issued May 16, 1996;

U.S. Pat. No. 5,704,965 issued Jan. 6, 1998;

U.S. Pat. No. 5,704,967 issued Jan. 6, 1998;

U.S. Pat. No. 5,707,424 issued Jan. 13, 1998; and

U.S. Pat. No. 5,917,140 issued Jun. 29, 1999.

The present invent ion provides a gas cabinet assembly including a newatmospheric pressure storage and delivery system apparatus as a sourcegas supply means for applications such as ion implantation of hydrideand halide gases, and organometallic Group V compounds, e.g., arsine,phosphine, chlorine, NF₃, BF₃, BCl₃, diborane (B₂H₆ and its deuteriumanalog, B₂D₆), HCl, HBr, HF, HI, tungsten hexafluoride, and (CH₃)₃Sb.The new gas source system is comprised of a leak-tight gas vessel, suchas a gas cylinder, containing the gas to be dispensed, e.g., arsine orphosphine, adsorbed into a sorbent material comprising zeolite or othersuitable physical adsorbent material. In the case of arsine andphosphine, the zeolite reduces the vapor pressure of the arsine andphosphine to 1 atmosphere.

Since the storage and delivery system is initially at atmosphericpressure, the release rate is controlled primarily by diffusion insteadof a pressure differential. Inadvertent releases from the storage anddelivery system have been measured and result in exposure concentrationsto <½ IDLH. Release rate comparisons of the storage and delivery systemto standard cylinders are more fully discussed hereinafter, anddemonstrate that the storage and delivery system apparatus and method ofthe present invention is about 1×10⁵ safer than compressed gas sources.

While the invention is discussed primarily hereinafter in terms of thestorage and delivery of arsine and phosphine gases, it will berecognized that the utility of the present invention is not thuslimited, but rather extends to and is inclusive of various other hydrideand halide gases, as for example silane, diborane, arsine, phosphine,chlorine, BCl₃, BF₃, B₂D₆, tungsten hexafluoride, hydrogen fluoride,hydrogen chloride, hydrogen iodide, hydrogen bromide, germane, ammonia,stibine, hydrogen sulfide, hydrogen selenide, hydrogen telluride, andcorresponding and other halide (chlorine, bromine, iodine, and fluorine)gaseous compounds such as NF₃, and organometallic compounds, e.g., GroupV compounds such as (CH₃)₃Sb.

The novel means and method of the present invention for storing anddelivering gaseous arsine and phosphine at 0 psig greatly reduces thehazard posed by these gases. The technique involves the adsorption ofthese gases into a physical adsorbent such as, for example, zeolite 5A.By adsorbing the gas into a zeolite or other suitable soild physicalsorbent, the vapor pressure of the gas can be reduced to 0 psig. Therelease potential from this system is greatly reduced as the drivingforce of pressure is eliminated. Collectively, the storage and deliverysystem may usefully consist of a standard gas cylinder and cylindervalve, loaded with dehydrated zeolite 5A. The cylinder is subsequentlyfilled to 1 atmosphere with the hydride gas. Although primarilydisclosed hereinafter in reference to zeolites, the invention is broadlyapplicable to the usage of a wide variety of other physical sorbentmaterials, such as kieselguhr, silica, alumina, macroreticulate polymers(e.g., Amberlite resins, available from Rohm & Haas Company,Philadelphia, Pa.), carbon (e.g., bead activated carbon), etc.

Zeolites are microporous crystalline aluminosilicates of alkali oralkaline earth elements represented by the following stoichiometry:

M_(x/n)[(AlO₂)_(x)(SiO₂)_(y)]zH₂O

where x and y are integers with y/x=to or greater than 1, n is thevalence of the cation M and z is the number of water molecules in eachunit cell. Zeolite 5A has ˜2.5×10²¹ hydride adsorption sites per gram. Aliter of zeolite will adsorb 100 grams of phosphine and 220 grams ofarsine at 25° C. and 1 atmosphere. FIGS. 1 and 2 show the adsorptionisotherms for arsine and phosphine, respectively.

These isotherms show vapor pressure as a function of adsorbed hydridefor a 1 liter cylinder. The isotherms are useful in determining theamount of deliverable hydride gas. As seen from the isotherms, roughly50% of the hydride is adsorbed between 50-760 Torr. This is the amountof hydride that can practically be delivered by the respective storageand delivery systems.

Gas flow from the storage and delivery system is established using theexisting pressure differential between the storage and delivery systemand the ion implant vacuum chamber or other downstream use locus.Utilizing a device such as a mass flow controller, a constant flow canbe achieved as the sorbent container pressure decreases.

An appropriate delivery system for a zeolite storage system according tothe invention is shown in FIG. 3.

In the schematic storage and delivery system shown in FIG. 3, a gasstorage cylinder 10 is provided which may be filled with a bed ofsuitable physical adsorbent material, e.g., a zeolite sorbent or othersuitable physical adsorbent medium of a type as more fully describedhereinabove. The gas cylinder 10 is provided therein with the physicaladsorbent bearing a physically adsorbed gas component, or components,such as arsine or phosphine.

The cylinder 10 is connected to a manifold 12, having disposed therein acylinder valve 14 for controllably releasing gas from cylinder 10,upstream of a gas cylinder isolation valve 16, which may be selectivelyactuated to close cylinder 10 to communication with the manifold 12.

The manifold has a branch fitting 18 therein, by means of which themanifold 12 is coupled in gas flow communication with a branch purgeline 20 having inert gas purge isolation valve 22 therein, whereby themanifold may be purged with inert gas, prior to active operationdelivery of gas from cylinder 10.

Downstream from the fitting 18, the manifold contains two successive gasfilters 28 and 30, intermediate of which is disposed a pressuretransducer 32 which may, for example, have a pressure operating range offrom about 0 to about 25 psia.

The manifold 12 is connected downstream of gas filter 30 with a branchfitting 34 to which is coupled a bypass conduit 36 having bypassisolation valve 38 therein.

The manifold 12 downstream of fitting 34 has a gas flow on-off valve 40therein, downstream of which is disposed a mass flow controller 42 forcontrollably adjusting the flow rate of the hydride or halite gasdispensed through manifold 12. At its terminus downstream of mass flowcontroller 42, the manifold 12 is connected by coupling fitting 44 todispensing line 46 filing flow control valve 48 therein, and also beingcoupled in gas flow communication with bypass line 36 via couplingfitting 50. The discharge line 46 is as shown joined to an ion sourcegenerating means, schematically shown as element 52. The other end 54 ofdischarge line 46 may be suitably coupled in gas flow communication withanother gas dispensing means, as desirable or necessary in a given enduse application of the FIG. 3 storage and delivery system apparatus.

FIG. 4 shows the delivery lifetime of a 4X molecular sieve (2.35 liters)in an arsine storage and delivery system apparatus to be ˜1000 hr. at aflow rate of 1 sccm.

The lifetime test was conducted using a storage and delivery systemapparatus similar to that schematically shown in FIG. 3.

In addition to the safety advantages, the zeolite storage technology ofthe present invention allows for a greater quantity of delivered gas.Table 1 below shows a comparison of delivered hydride from typical highpressure sources to that of the storage and delivery system.

TABLE 1 Delivery comparison of storage and delivery system cylinders toa standard high pressure cylinder (grams delivered) 400 PSIG 15% 440 ml2.3 Liter storage/delivery Gas storage/delivery system system Arsine 640 225 Phosphine 3 18 105

Since approximately 5-20 times as much hydride is delivered by thestorage and delivery system than by standard cylinders, fewer cylinderchanges are required, thereby yielding enhanced productivity of theimplant tool. Additionally, since most accidents with gases occur duringcylinder changes, safety is further improved.

Since the storage and delivery system operates in the sub-atmosphericregime, the safety aspects related to an accidental incursion of airinto a phosphine storage and delivery system cylinder was investigated.Phosphine spontaneously reacts with air as shown in the followingequation:

4PH₃+8O₂→P₄O₁₀+6H₂O

H_(f) of P₄O₁₀=−720 Kcal/mole

A threshhold concern and intuitive expectation is that the excessiveheat of reaction would cause a large pressure excursion or even adetonation in the cylinder. However, it has been determined that theevent of ingressing air is of a manageable character since most of theresultingly generated heat will be adsorbed by the zeolite substrate.FIG. 5 shows the temperature and pressure rise during the experimentalbackfilling of a 0.5 liter phosphine storage and delivery system withroom air, as a plot of cylinder pressure, in Torr, as a function oftime, in seconds.

In the FIG. 5 system, the initial pressure of the phosphine storage anddelivery system was 50 Torr. Upon backfilling, the reaction temperaturewas monitored with a thermocouple located inside the storage anddelivery system cylinder. The reaction with air caused a temperaturerise of 35° C. inside the cylinder. The cylinder pressure was measuredusing a capacitance pressure transducer. The maximum pressure recordedwas ˜800 Torr. The pressure rise above 1 atmosphere is a result of theincreased bed temperature. The experimental data left us to concludethat the air backfill of a partially used phosphine storage and deliverysystem is not a significant safety hazard. The arsine case was notinvestigated as arsine reacts slowly with air at room temperature.

Hydride release was measured in a storage and delivery system apparatusof the type shown in FIG. 3 and described hereinabove. The emission rateof arsine from the storage and delivery system was measured and found tobe 3.8 milligrams/minute. Although small, such rate was 3 orders ofmagnitude larger than that calculated from diffusion equations. It issuspected that the apparatus used in this experiment gave an erroneouslyhigh emission rate due to an eduction effect. Nonetheless, thisexperiment gives a worst case emission rate that is still 10⁻⁵ timesless than a standard high pressure cylinder. FIG. 6. shows the emissionrate of a standard gas cylinder versus an arsine storage and deliverysystem.

The purity of the arsine and phosphine from the storage and deliverysystem of the instant invention is exceptional. The only significantimpurity detected is H₂. The hydrogen levels are found to vary between10-1000 ppm. Since H₂ is currently used as a diluent in high pressurecylinders its presence is non-problematic in terms of operationalefficacy of the storage and delivery system apparatus and method. Gaschromatography and mass spectroscopy have been used to verify the purityof the hydride.

The storage and delivery system-delivered arsine and phosphine is fullycompatible with the ion implantation process. Yield analyses of wafersfrom split lots have been shown to be identical for those implanted withAs and P from the storage and delivery system compared with thoseimplanted with As and P from standard sources.

The storage and delivery system apparatus and method of the inventionthus provide a significantly safer alternative to the current use ofhigh pressure gas cylinders for the storage and dispensing of hydrideand halide gases. The invention provides the capability to transport,store and deliver hydrides from a cylinder or other vessel at zero psig.The invention is based on the discovery that hydride and halide gasescan be physically adsorbed into the microcavities of suitable supportmaterials such as zeolites, thereby significantly reducing the pressureof gas for storage and dispensing purposes.

With only low level heating of the sorbent material in the practice ofthe present invention, by so-called thermally assisted delivery, it ispossible to augment the delivery rate of the desorbing gas, so that flowrates of up to 500 sccm and higher are readily achieveable. Nonetheless,high rates of gas delivery are achieved in the broad practice of thepresent invention with adiabatic operation (no supplemental input ofheat or thermal energy to the sorbate-laden sorbent medium), solely bythe pressure differential existing between the sorbent vessel and thereduced pressure of the semiconductor (or other industrial ormanufacturing) process, such as ion implantation, molecular beamepitaxy, and chemical vapor deposition.

The apparatus of the present invention may be readily provided in aunitary apparatus form, as disposed in a gas cabinet containing amultiplicity, e.g., three, sorbent vessels, each manifolded together forselective delivery of sorbate gas from one or more of such vessels. Thecabinet may further include therein independent thermocouples, or othertemperature sensing/monitoring equipment and components for preventingoverheating of the vessels and/or other internal components of the gascabinet in use thereof.

The cabinet may additionally include a fusible link heater element forselective augmentive heating of the vessels and sorbent therein; asprinkler system; an exhaust heat sensor; a toxic gas monitor whichfunctions to shut down the apparatus when toxic gas is sensed; ascrubber or bulk sorption device; and redundant pressure and temperaturecontrol means. With such a storage and delivery system apparatus,delivery rates of gas of 500 sccm at 15 psig are readily attainable.

In the preferred practice of the invention, the solid-phase physicalsorbent medium is devoid of trace components selected from the groupconsisting of water, metals, and oxidic transition metal species in aconcentration which is insufficient to decompose the sorbate gas in saidstorage and dispensing vessel. A highly advantageous sorbent medium ofsuch type is commercially available from Zeochem Company (Louisville,Ky.) as Zeochem Binderless 5A sorbent, which is a synthetic calciumaluminosilicate of the formula (CaO.Na₂O).Al₂O₃.2SiO₂.xH₂O.

In this respect, it is to be noted that the significant presence in thesorbent material of any water, metals, or transition metal oxides tendsto promote undesirably high levels of decomposition of the sorbate gas.In molecular sieves and other materials which lack such “contaminants”the sorbate gas degradation levels, and corresponding pressure levelsare maintained at correspondingly low values. Concerning molecular sievematerials most specifically, a large number of such sorbents invariablycontain clay or other mineralic binders which contain the aforementioneddecomposition promotors, which undesirably degrade the performance ofthe storage and delivery system apparatus and method.

By way of example, the above-mentioned binderless Zeochem material hasno detectable metallic impurities, while other conventional molecularsieve materials, e.g., Linde 5A zeolite has a substantial amount of irontherein. In consequence, the binderless zeolite exhibits decompositionlevels which are on the order of about 1-2% of arsine (in an arsinestorage and delivery system apparatus containing such zeolite) per year,while the Linde 5A zeolite exhibits decomposition levels of arsine whichare on the order of a few tenths of a percent of the arsine per day.With the binderless zeolite, pressure increases in the sorbentmaterial-containing vessel are less than 5% per week, while the Linde 5Azeolite (containing binder metal components) exhibits pressure rises of9 psig (60%) per day in a corresponding storage and delivery systemapparatus.

The solid-phase physical sorbent medium in the preferred practice of theinvention therefore contains less than 350 parts-per-million by weightof trace components selected from the group consisting of water andoxidic transition metal species, based on the weight of the physicalsorbent medium, more preferably less than 100 parts-per-million byweight, still more preferably less than 10 parts-per-million, and mostpreferably no more than 1 part-per-million by weight of trace componentsselected from the group consisting of water and oxidic transition metalspecies, based on the weight of the physical sorbent medium.

Correspondingly, the solid-phase physical sorbent medium concentrationof trace components selected from the group consisting of water andoxidic transition metal species (e.g., oxides, sulfites and nitrates),based on the weight of the physical sorbent medium, preferably isinsufficient to decompose more than 5% by weight of the sorbate gasafter 1 year at 25° C. and said interior pressure.

In some applications, it is desired to provide gases deriving from astorage and delivery system apparatus at a higher-than-dischargepressure from the storage and delivery system sorbent-containing vessel.In such instances, venturi pumps may be employed which raise thepressure of the supplied gas to a selected pressure level above that atthe cylinder head (of the cylinder containing the sorbent binding thegas being dispensed). Although such venturi pumping arrangements yieldthe dispensed gas at the selected higher pressure level, sucharrangements nonetheless entail dilution of the gas being dispensed witha carrier gas, since the carrier gas is entrained with the dispensed gasfrom the cylinder.

Such dilution effect represents a significant constraint on the overallprocess system, in instances where neat gas of high purity is desiredfrom the storage and delivery system apparatus. Mechanical pumps may beused in place of venturi pumping means, but mechanical pumps entail thedisadvantage of a significant number of moving parts, which can causeproblems associated with the formation of particulates in the pumpand/or entrainment of lubricants.

In such instances, where the gas supplied by the storage and deliverysystem apparatus is desired to be furnished at high pressure in a highpurity, neat condition, the provision of a cryopumping assembly in thestorage and delivery system apparatus may be advantageous.

FIG. 7 is a schematic perspective view of such a cryopumping storage anddelivery system apparatus 100, according to a further embodiment of theinvention.

In the cryopumping system, the main cylinder 102 contains a suitablesorbent material (not shown), e.g., molecular sieve, having loadedthereon a suitable sorbate gas species to be subsequently dispensed, andis equipped with a valve head assembly 104 including main cylinder valve106, which is in the ♭off? position at the start of the dispensingprocess.

The valve head 104 is coupled to conduit 108 containing isolation valve110, mass flow controller 112, isolation valve 114, and cryopump 116.Conduit 108 is in turn coupled to conduit 109 containing isolationvalves 118 and 122 and product dispensing regulator assembly 130 havingdischarge port 134 coupleable to a downstream process system. Joined tothe conduit 109 is a medium pressure storage vessel 120.

The cryopump 116 coupled to conduit 108 is provided with a liquidnitrogen (or other suitable cryogenic liquid or fluid) inlet 128 and aliquid nitrogen outlet 126, with a liquid cryogen flow path beingprovided intermediate the inlet 128 and the outlet 126 which iscircumscribed by heating elements 124 as shown. The liquid cryogen inletand outlet of the cryopump may be suitably joined to a source of liquidcryogen, as for example a cryogenic air separation installation or acryogenic cylinder source of liquid nitrogen or other coolant. Thecryopump thereby forms a cryotrap apparatus. The outlet of the cryopumpthus is provided with an isolation valve 122, and the medium pressurecylinder 120 is isolatable by means of the isolation valve 122.

A pressure transducer 111 is provided in conduit 108 and is coupled inpressure monitoring relationship to cylinder 102 for monitoring ofpressure in the cylinder and responsively adjusting the isolation valve118.

The operation of the storage and delivery system shown schematically inFIG. 7 is illustrated below with reference to silane as the gas sorbedon the sorbent in cylinder 102 and to be delivered at suitable elevatedpressure, and nitrogen as the cryogen to be employed as the workingfluid in the cryopump 116. Silane has a boiling point of −111.5 degreesCentigrade and a melting point of 185 degrees Centigrade, and nitrogenhas a boiling point of −195.8 degrees Centigrade.

Silane has been selected for illustration purposes since it isrelatively difficult to deliver at suitably elevated pressure (inrelation to other hydridic gases such as arsine which have higherboiling and freezing points, and thus may be more easily cryopumped withless cryogenic cooling being required).

If at the outset valves 110, 114, and 106 are open, with valves 118 and122 being closed and under vacuum, and the temperature in the cryogenicpump is lowered to liquid nitrogen temperatures, silane will condenseand freeze in the cryopump, even if relatively low internal pressuresexist in the supply cylinder 102.

The mass flow controller 112 allows for accurate determination of thequantity of gas being transferred to the cryopump 116. Such accuratedetermination is important because overpressurization of the cryopump isdesirably avoided. Under such operating conditions, silane will be aboveits critical temperature so that the ultimate pressure in the cryopumpcan potentially become very high.

After the correct amount of gas has been transferred to the cryopump116, the valves 110 and 114 are closed. The condensed silane then iswarmed to near ambient temperatures. The heating is carried out by theheating means 124, which in the embodiment shown comprise band heatersbut could be any suitable heating means appropriate for such service.The silane gas does not thereby have to be heated to high temperatures,and the stability and purity of the product gas to be dispensed isthereby enhanced, since heating may result in the occurence ofdegradation of the silane gas with consequent adverse effect on itspurity and further stability.

The pressure of the silane gas after the warm-up in the cryopump maybecome significantly elevated, and effectively the gas thereby hasbecome compressed, in a high purity state, and without exposure to amechanical pump with many moving parts which may otherwise result incontamination of the product gas.

The inventory of gases in the overall system may be quite low at thispoint, with most of the silane residing in the sorbent vessel, cylinder102, at low pressure.

Opening valve 118 will then allow gas to flow into the medium pressurecylinder 120; if valve 122 is open, then product silane gas can flow tothe downstream process through discharge port 134, as monitored by themonitoring means (e.g., flow pressure) associated with the regulatorassembly 130. The regulator assembly 130 has associated pressuretransducer 132 which may be operatively coupled in the overall systemwith the other valves and cryopump components so that the product gas isdelivered at a selected pressure and volumetric flow rate.

Correspondingly, the various valves, mass flow controller, cryopump,transducers and regulator may be operatively interconnected in anysuitable manner, e.g., with cycle timer, and process safety systems, tocarry out the demand-based delivery of silane or other sorbate gases, ina readily controllable and reproducible manner.

Accordingly, the operation of the system schematically shown in FIG. 7desirably is timed to avoid disruption to or interference withdownstream process flows. Signals from the mass flow controller andpressure transducers in the cryopump and medium pressure tanks can beused in an automated process system. The cryopump can be cycled to movegases from the storage and delivery system to the medium pressurecylinder 120 to maintain a constant pressure at the outlet of theregulator.

EXAMPLE I

Decomposition of arsine gas in a storage and delivery cylinder wascomparatively evaluated for each of two molecular sieve sorbentmaterials: Linde 5A molecular sieve (Union Carbide Corporation, Danbury,Conn.), hereinafter referred to as Sorbent A, and Zeochem 5A molecularsieve (Zeochem, Louisville, Ky.), hereinafter referred to as Sorbent B.Each of Sorbent A and Sorbent B are synthetic crystalline calciumaluminosilicates having 5 Angstrom pore size, but Sorbent A contains aclay binder whereas Sorbent B is binderless.

Set out in Table II below is a quantitative analysis of the Sorbent Aand Sorbent B showing the differences in composition thereof, where thepart-per-million (ppm) concentrations listed are ±50%.

TABLE II Quantitative Analysis of Sorbent A and Sorbent B, inparts-per-million (ppm) Sorbent A Sorbent B Aluminum major^(a) majorBarium <372 <301 Beryllium <372 <301 Calcium major major Cobalt <372<301 Chromium <372 <301 Copper <372 <301 Iron 3084 <301 Gallium <372<301 Magnesium  556 <301 Manganese <372 <301 Molybdenum <372 <301 Nickel<372 <301 Phosphorus <372 <301 Lead <372 <301 Silicon major major Tin<372 <301 Strontium <372 <301 Titanium <372 <301 Vanadium <372 <301 Zinc<372 <301 Zirconium <372 <301 % Silicon 21.19 19.70 % Aluminum 19.1117.39 % Calcium   7.21  7.45 ^(a)major here referring to at least 5% byweight, based on the total weight of the molecular sieve

As shown by the data in Table II, Sorbent B contained trace amounts(defined here as amounts of less than about 500 ppm of the specifiedcomponent) of all measured elements with the exception of the majorcomponents of the molecular sieve, calcium, aluminum, and silicon, whileSorbent A contained a significant amount of iron (3084 ppm) and slightlymore than a trace amount of magnesium.

In the comparison test of the two sorbent materials, each of identicalgas cylinders was filled with a respective sieve material (Sorbent A ina first cylinder and Sorbent B in a second cylinder), and the sievematerials in each of the cylinders was loaded with a same amount ofarsine gas. After the loading of the sieve materials in the respectivecylinders, the pressures in each of the cylinders was monitored forpressure rise due to decomposition of arsine by the reaction As As+1.5H₂, since hydrogen is not adsorbed by the molecular sieves. Suchmonitoring took place at constant temperature.

The resulting pressure history as a function of time is shown in thegraph of FIG. 8, in which the pressure in psia is plotted as a functionof elapsed time, in minutes. As shown by the Figure, curve A, showingthe pressure behavior of the gas in the cylinder containing Sorbent A,after 250 hours rose to approximately 37.5 psia, while curve B, showingthe pressure behavior of the gas in the cylinder containing Sorbent B,shows no pressure rise over the same period of time of the test.

The performance differences exhibited by the respective Sorbents A and Bis striking, for the fact that while otherwise compositionallyequivalent, the fact of the more-than-trace concentration of iron inSorbent A led to substantially increased pressure due to thedecomposition of arsine in the cylinder containing Sorbent A, whileSorbent B maintained the arsine in an undecomposed state, with noformation of hydrogen being observed in respect of pressure increase.

Accordingly, it is a significant discovery that the decomposition ofhydridic gases such as arsine, phosphine, etc., can be suppressed by theprovision of sorbent materials which are devoid of more than traceamounts of contaminants such as iron, which are conventionally presentin commercially available molecular sieves and other sorbent materialscomprising mineralic or clay-based binders, which have been incorporatedin the sorbent composition for enhancing the structural stability andintegrity of the sorbent material.

FIG. 9 is a frontal perspective view of a gas cabinet assembly 400incorporating a sorbent-based gas storage and dispensing assemblyaccording to one embodiment of the invention.

The gas cabinet assembly 400 includes a gas cabinet 402. The gas cabinet402 has side walls 404 and 406, floor 408, rear wall 410 and ceiling 411defining a housing with front doors 414 and 420. The housing andrespective doors enclose an interior volume 412.

The doors may be arranged to be self-closing and self-latching incharacter. For such purpose, the door 414 may have a latch element 418that cooperatively engages lock element 424 on door 420. The doors 414and 420 may be beveled and/or gasketed in such manner as to produce agas-tight seal upon closure of the doors.

The doors 414 and 420 as shown may be equipped with windows 416 and 422,respectively. The windows may by wire-reinforced and/or tempered glass,so as to be resistant to breakage, while at the same time being ofsufficient area to afford an unobstructed view of the interior volume412 and manifold 426.

The manifold 426 as shown may be arrranged with an inlet connection line430 that is joinable in closed flow communication with gas supply vessel433.

The manifold 426 may comprise any suitable components, including forexample flow control valves, mass flow controllers, process gasmonitoring instrumentation for monitoring the process conditions of thegas being dispensed from the supply vessel, such as pressure,temperature, flow rate, concentration, and the like, manifold controls,including automated switching assemblies for switchover of the gassupply vessels when a multiplicity of such vessels is installed in thegas cabinet, leak detection devices, automated purge equipment andassociated actuators for purging the interior volume of the gas cabinetwhen a leak is detected from one or more of the supply vessels.

The manifold 426 connects to an outlet 428 at the wall 404 of thecabinet, and the outlet 428 may in turn be connected to piping forconveying the gas dispensed from the supply vessel to a downstreamgas-consumption unit coupled with the gas cabinet. The gas-consumptionunit may for example comprise an ion implanter, chemical vapordeposition reactor, photolithography track, diffusion chamber, plasmagenerator, oxidation chamber, etc. The manifold 426 may be constructedand arranged for providing a predetermined flow rate of the dispensedgas from the supply vessel and gas cabinet to the gas-consumption unit.

The gas cabinet has a roof-mounted display 472 coupled with the manifoldelements and ancillary elements in the interior volume of the cabinet,for monitoring the process of dispensing the gas from the gas supplyvessel(s) in the interior volume of the cabinet.

The gas cabinet may also be provided with a roof-mounted exhaust fan 474that is coupled by coupling fitting 476 to discharge conduit 478 fordischarge of gas from the interior volume of the cabinet, in thedirection indicated by arrow E. The exhaust fan 474 may be operated atappropriate rotational speed to impose a predetermined vacuum ornegative pressure in the interior volume of the cabinet, as a furtherprotective measure against any undesirable efflux of gas leakage fromthe gas cabinet. The discharge conduit may therefore be coupled to adownstream gas treatment unit (not shown), such as a scrubber orextraction unit for removing any leakage gas from the exhaust stream. Inorder to provide a supply of inflowing air for such purpose, thecabinet, e.g., the doors, may be constructed to allow a net inflow ofambient air as a sweep or purge stream for clearing the interior volumegas from the cabinet. Thus, the doors may be louvered, or otherwise beconstructed for ingress of ambient gas.

The gas supply vessel 433 may suitably comprise a leak-tight gascontainer, such as for example a cylindrical container of the type usedin conventional high pressure gas cylinders, including a wall 432enclosing an interior volume of the vessel. Disposed in the interiorvolume of the container is a particulate solid sorbent medium, e.g., aphysical adsorbent material such as carbon, molecular sieve, silica,alumina, etc. The sorbent may be of a type as described hereinabove,which has a high sorptive affinity and capacity for the gas to bedispensed.

For applications such as semiconductor manufacturing, in which dispensedreagent gases are preferably of ultra-high purity, e.g., “7-9's” purity,more preferably “9—9's” purity, and even higher, the sorbent materialmust be substantially free, and preferably essentially completely free,of any contaminant species that would cause decomposition of the storedgas in the vessel and cause the vessel interior pressure to rise tolevels significantly above the desired set point storage pressure.

For example, it is typically desirable to utilize the sorbent-basedstorage and dispensing vessel of the invention to retain gas in thestored state at pressure not exceeding about atmospheric pressure, e.g.,in the range of from about 25 to about 800 torr. Such atmospheric orbelow atmospheric pressure levels provide a level of safety andreliability that is lacking in the use of high pressure compressed gascylinders.

For such high purity gas dispensing operation from the sorbent-basedstorage and dispensing system of the invention, it is desirable that thesupply vessel be subjected to suitable preparative operations, such asvessel bake-out, and/or purging, to ensure that the vessel itself isfree of contaminants that may outgas or otherwise adversely affect thegas dispensing operation in subsequent use of the sorbent-based storageand dispensing system. Further, the sorbent itself may be subjected toappropriate preparative operations, such as pretreatment to ensuredesorption of all extraneous species from the adsorbent material, priorto being loaded in the supply vessel, or alternatively of beingsubjected to bake-out and/or purging after the adsorbent is charged tothe vessel.

As shown in FIG. 9, the supply vessel 433 is of elongate verticallyupstanding form, having a lower end that is reposed on the floor 408 ofthe cabinet, and with an upper neck portion 436 to which is secured avalve head 438 to leak-tightly seal the vessel. In its fabrication, thesupply vessel 433 may be filled with adsorbent and thereafter, before orafter the sorbate gas is loaded on the sorbent, the valve head 438 maybe secured to the vessel neck portion, e.g., by welding, brazing,soldering, compressive joint fixturing with a suitable sealant material,etc., so that the vessel thereafter is leak-tight in character at theneck joint with the valve head.

The valve head 438 is provided with a coupling 442 for joining thevessel to suitable piping or other flow means permitting selectivedispensing of gas from the vessel. The valve head may be provided with ahand wheel 439 for manually opening or closing the valve in the valvehead, to flow or terminate the flow of gas into the connecting piping.Alternatively, the valve head may be provided with an automatic valveactuator that is linked to suitable flow control means, whereby the flowof gas during the dispensing operation is maintained at a desired level.

In operation, a pressure differential between the interior volume of thesupply vessel 433 and the exterior piping/flow circuitry of the manifoldis established to cause gas to desorb from the sorbent material and toflow from the vessel into the gas flow manifold 426. A concentrationdriving force for mass transfer is thereby created, by which gas desorbsfrom the sorbent and passes into the free gas volume of the vessel, toflow out of the vessel while the valve in the valve head is open.

Alternatively, the gas to be dispensed may be at least partiallythermally desorbed from the sorbent in the vessel 433. For such purpose,the floor 408 of the cabinet may have an electrically actuatableresistance heating region on which the vessel is reposed, so thatelectrical actuation of the resistance heating region of the floorcauses heat to be transferred to the vessel and the sorbent materialtherein. As a result of such heating, the stored gas desorbs from thesorbent in the vessel and may be subsequently dispensed.

The vessel may alternatively be heated for such purpose by deployment ofa heating jacket or a heating blanket that enwraps or surrounds thevessel casing, so that the vessel and its contents are appropriatelyheated to effect the desorption of the stored gas, and subsequentdispensing thereof.

As a further approach, the desorption of the stored gas in the vesselmay be carried out under the impetus of bothpressure-differential-mediated desorption and thermally-mediateddesorption.

As yet another alternative, the supply vessel may be provided with acarrier gas inlet port 449, which may be connected to a source ofcarrier gas (not shown) either interior or exterior to the cabinet. Suchgas source may provide a flow of suitable gas, e.g., an inert gas orother gas that is non-deleterious to the process in the downstreamgas-consumption unit. In such manner, gas may be flowed through thevessel to cause a concentration gradient to be developed that willeffect desorption of the sorbate gas from the sorbent in the vessel. Thecarrier gas may therefore be a gas such as nitrogen, argon, krypton,xenon, helium, etc.

As shown in FIG. 9, the supply vessel 433 is held in place in the gascabinet by strap fastners 446 and 448 of a conventional type. Otherfasteners could be used, such as neck rings, or other securementstructures may be employed, such as receiving depressions or cavities inthe floor of the gas cabinet, that matably receive the lower end of thevessel therein, guide members or compartment structures that fixedlyretain the vessel in a desired position in the interior volume of thegas cabinet.

Although only one vessel 433 is shown in the gas cabinet in FIG. 9, suchgas cabinet is shown as being constructed and arranged to retain one,two or three vessels therein. In addition to the vessel 433, an optionalsecond vessel 460 and an optional third vessel 462 are shown in dashedline representation in FIG. 9, being associated with the respectivestrap fasteners 464 and 466 (for optional vessel 460) and strapfasteners 468 and 470 (for optional vessel 462).

It will be apparent that the gas cabinet of the invention may be widelyvaried, to contain one or more than one vessel therein. In such manner,any number of gas supply vessels can be retained in a single unitaryenclosure, thereby providing enhanced safety and process reliability inrelation to use of conventional high pressure compressed gas cylinders.

In such manner, a multiplicity of sorbent-containing gas supply vesselsmay be provided, for sourcing of the various gas components needed inthe downstream gas-consumption unit, or to provide multiple vessels eachcontaining the same gas. The gases in multiple vessels in the gascabinet may thus be the same as or different from one another, and therespective vessels may be concurrently operated to extract gas therefromfor the downstream gas-consumption unit, or the respective vessels maybe operated by a cycle timer program and automated valve/manifoldoperation means, to successively open the vessels in turn to providecontinuity of operation, or otherwise to accommodate the processrequirements of the downstream gas-consumption unit.

The display 472 may be programmatically arranged with associatedcomputer/microprocessor means to provide visual output indicative of thestatus of process operation, the volume of the dispensed gas floweddownstream, the remaining time or gas volume for the dispensingoperation, etc. The display may be arranged to provide output indicatingthe time or frequency of maintenance events for the cabinet, or anyother suitable information appropriate to the operation, use andmaintenance of the gas cabinet assembly.

The display may also comprise audible alarm output means, signalling theneed for changeout of the vessels in the gas cabinet, a leakage event,approach of cycle termination, or any event, state or process conditionthat is useful in the operation, use and maintenance of the gas cabinet.

It will therefore be appreciated that the gas cabinet assembly of thepresent invention may be widely varied in form and function, to providea flexible means for sourcing reagent gas(es) to a downstreamgas-consumption unit, such as a process unit in a semiconductormanufacturing facility.

The present invention therefore has utility in the manufacture ofsemiconductor materials and devices, and in other gas-consuming processoperations, where it provides a reliable “on demand” source of gas,e.g., hydride gases, halide gases, and gaseous organometallic Group Vcompounds, including, for example, silane, diborane, germane, ammonia,phosphine, arsine, stibine, hydrogen sulfide, hydrogen selenide,hydrogen telluride, boron trifluoride, tungsten hexafluoride, chlorine,hydrogen chloride, hydrogen bromide, hydrogen iodide, and hydrogenfluoride.

By providing an economical and reliable source of such gases, in whichthe gas is safely held at relatively low pressure in the adsorbed stateon a sorbent medium, and subsequently is easily dispensed to the pointof use of the gas, the present invention avoids the hazards and gashandling problems associated with the use of conventional high pressuregas cylinders.

What is claimed is:
 1. A process for supplying a gas reagent,comprising: providing a storage and dispensing vessel containing asolid-phase physical sorbent medium having a physically sorptiveaffinity for said gas reagent; physically sorptively loading on saidsolid-phase physical sorbent medium a sorbate gas, to yield a sorbategas-loaded physical sorbent medium; mounting the storage and dispensingvessel in a gas cabinet defining an enclosure including therein a gasdispensing manifold; coupling the gas storage and dispensing vessel ingas flow communication with the gas dispensing manifold; selectivelydesorbing sorbate gas from the sorbate gas-loaded physical sorbentmedium, by reduced pressure desorption, for flow of desorbed sorbate gasinto the gas dispensing manifold and dispensing thereof; wherein thesolid-phase physical sorbent medium is devoid of trace componentsselected from the group consisting of water. metals and oxidictransition metal species in a sufficient concentration to decompose thesorbate gas in said storage and dispensing vessel.
 2. A processaccording to claim 1, wherein the solid-phase physical sorbent mediumcontains less than 350 parts-per-million by weight of trace componentsselected from the group consisting of water and oxidic transition metalspecies, based on the weight of the physical sorbent medium.
 3. Aprocess according to claim 1, wherein the solid-phase physical sorbentmedium contains less than 100 parts-per-million by weight of tracecomponents selected from the group consisting of water and oxidictransition metal species, based on the weight of the physical sorbentmedium.
 4. A process according to claim 1, wherein the solid-phasephysical sorbent medium contains no more than 1 part-per-million byweight of trace components selected from the group consisting of waterand oxidic transition metal species, based on the weight of the physicalsorbent medium.
 5. A process according to claim 1, wherein thesolid-phase physical sorbent medium concentration of trace componentsselected from the group consisting of water and oxidic transition metalspecies, based on the weight of the physical sorbent medium, isinsufficient to decompose more than 5% by weight of the sorbate gasafter 1 year at 25° C. and said interior pressure.
 6. A processaccording to claim 1, wherein the oxidic transition metal species areselected from the group consisting of oxides, sulfites and nitrates. 7.A process according to claim 1, wherein the sorbate gas is a hydridegas.
 8. A process according to claim 1, wherein the sorbate gas isselected from the group consisting of silane, diborane, arsine,phosphine, chlorine, BCl₃, BF₃, B₂D₆, tungsten hexafluoride, (CH₃)₃Sb,hydrogen fluoride, hydrogen chloride, hydrogen iodide, hydrogen bromide,germane, ammonia, stibine, hydrogen sulfide, hydrogen selenide, hydrogentelluride, and NF₃.
 9. A process according to claim 1, wherein thesorbate gas is boron trifluoride.
 10. A process according to claim 1,further comprising selectively heating the solid-phase physical sorbentmedium, to effect thermally-enhanced desorption of the sorbate gas fromthe solid-phase physical sorbent medium.
 11. A process according toclaim 1, wherein the solid-phase physical sorbent medium comprises amaterial selected from the group consisting of silica, carbon molecularsieves, alumina, macroreticulate polymers, kieselguhr, carbon, andaluminosilicates.
 12. A process according to claim 11, wherein thecrystalline aluminosilicate composition comprises a binderless molecularsieve.
 13. A process according to claim 1, wherein the solid-phasephysical sorbent medium comprises a crystalline aluminosilicatecomposition.
 14. A process according to claim 13, wherein thecrystalline aluminosilicate composition has pore size in the range offrom about 4 to about 13 Angstroms.
 15. A process according to claim 13,wherein the crystalline aluminosilicate composition comprises 5Amolecular sieve.
 16. A process according to claim 1, wherein thesolid-phase physical sorbent medium is present in said storage anddispensing vessel with a chemisorbent material having a sorptiveaffinity for contaminants of said sorbate gas therein.
 17. A processaccording to claim 16, wherein the chemisorbent material has a sorptiveaffinity for non-inert atmospheric gases.
 18. A process according toclaim 16, wherein the chemisorbent material comprises a scavengerselected from the group consisting of: (A) a scavenger including asupport having associated therewith, but not covalently bonded thereto,a compound which in the presence of said contaminant provides an anionwhich is reactive to effect the removal of said contaminant, saidcompound being selected from one or more members of the group consistingof: (i) carbanion source compounds whose corresponding protonatedcarbanion compounds have a pKa value of from about 22 to about 36; and(ii) anion source compounds formed by reaction of said carbanion sourcecompounds with the sorbate gas; and (B) a scavenger comprising: (i) aninert support having a surface area in the range of from about 50 toabout 1000 square meters per gram, and thermally stable up to at leastabout 250° C.; and (ii) an active scavenging species, present on thesupport at a concentration of from about 0.01 to about 1.0 moles perliter of support, and formed by the deposition on the support of a GroupIA metal selected from sodium, potassium, rubidium, and cesium and theirmixtures and alloys and pyrolysis thereof on said support.
 19. A processaccording to claim 16, wherein the chemisorbent material is selectedfrom the group consisting of potassium arsenide and trityllithium.
 20. Aprocess according to claim 1, wherein the sorbate gas comprises animpurity component, and the solid-phase physical sorbent medium isprovided in the storage and dispensing vessel together with an impurityscavenger for removal of the impurity component from the sorbate gas.21. A process for supplying a gas reagent, comprising: providing astorage and dispensing vessel containing a solid-phase physical sorbentmedium having a physically sorptive affinity for said gas reagent;physically sorptively- loading on said solid-phase physical sorbentmedium a sorbate gas, to yield a sorbate gas-loaded physical sorbentmedium; mounting the storage and dispensing vessel in a gas cabinetdefining an enclosure including therein a gas dispensing manifold;coupling the gas storage and dispensing vessel in gas flow communicationwith the gas dispensing manifold; and selectively desorbing sorbate gasfrom the sorbate gas-loaded physical sorbent medium, by reduced pressuredesorption, for flow of desorbed sorbate gas into the gas dispensingmanifold and dispensing thereof; wherein the solid-phase physicalsorbent medium concentration of trace components selected from the groupconsisting of water, metals, and oxidic transition metal species, basedon the weight of the physical sorbent medium, is insufficient to causedecomposition of the sorbate gas resulting in more than a 25% rise ininterior pressure after 1 week at 25° C. in said storage and dispensingvessel.
 22. A process according to claim 21, wherein the solid-phasephysical sorbent medium contains less than 350 parts-per-million byweight of trace components selected from the group consisting of waterand oxidic transition metal species, based on the weight of the physicalsorbent medium.
 23. A process according to claim 21, wherein thesolid-phase physical sorbent medium contains less than 100parts-per-million by weight of trace components selected from the groupconsisting of water and oxidic transition metal species, based on theweight of the physical sorbent medium.
 24. A process according to claim21, wherein the solid-phase physical sorbent medium contains no morethan 1 part-per-million by weight of trace components selected from thegroup consisting of water and oxidic transition metal species, based onthe weight of the physical sorbent medium.
 25. A process according toclaim 21, wherein the solid-phase physical sorbent medium concentrationof trace components selected from the group consisting of water andoxidic transition metal species, based on the weight of the physicalsorbent medium, is insufficient to decompose more than 5% by weight ofthe sorbate gas after 1 year at 25° C. and said interior pressure, insaid storage and dispensing vessel.
 26. A process according to claim 21,wherein the oxidic transition metal species are selected from the groupconsisting of oxides , sulfites and nitrates.
 27. A process according toclaim 21, wherein the sorbate gas is a hydride gas.
 28. A processaccording to claim 21, wherein the sorbate gas is selected from thegroup consisting of silane, diborane, arsine, phosphine, chlorine, BCl₃,BF₃, B₂D₆, tungsten hexafluoride, (CH₃)₃Sb, hydrogen fluoride, hydrogenchloride, hydrogen iodide, hydrogen bromide, ennane, ammonia, stibine,hydrogen sulfide, hydrogen selenide, hydrogen telluride, and NF₃.
 29. Aprocess according to claim 21, wherein the sorbate gas is borontrifluoride.
 30. An adsorption-desorption process for storage anddispensing of boron trifluoride, said process comprising: providing astorage and dispensing vessel containing a solid-phase physical sorbentmedium having a physically sorptive affinity for boron trifluoride;physically sorptively loading boron trifluoride on said solid-phasephysical sorbent medium, to yield a boron trifluoride-loaded physicalsorbent medium; mounting the storage and dispensing vessel in a gascabinet defining an enclosure including therein a gas dispensingmanifold; coupling the gas storage and dispensing vessel in gas flowcommunication with the gas dispensing manifold; and selectivelydesorbing boron trifluoride from the boron trifluoride-loaded physicalsorbent medium, by reduced pressure desorption, for flow of desorbedboron trifluoride gas into the gas dispensing manifold and dispensingthereof.
 31. A process for supplying a gas reagent, comprising:providing a storage and dispensing vessel containing a solid-phasephysical sorbent medium having a physically sorptive affinity for saidgas reagent; physically sorptively loading on said solid-phase physicalsorbent medium a sorbate gas, to yield a sorbate gas-loaded physicalsorbent medium; mounting the storage and dispensing vessel in a gascabinet defining an enclosure including therein a gas dispensingmanifold; coupling the gas storage and dispensing vessel in gas flowcommunication with a cryopump; coupling the cryopump in gas flowcommunication with the gas dispensing manifold; selectively desorbingsorbate gas from the sorbate gas-loaded physical sorbent medium, bypressure-differential mediated desorption, for flow of desorbed sorbategas to the cryopump; and cryopumping the desorbed gas from the storageand dispensing vessel to a predetermined pressure, wherein saidpredetermined pressure is higher than pressure of the desorbed gasflowed out of the storage and dispensing vessel.
 32. A gas supply systemcomprising: a gas cabinet defining an enclosure including therein a gasdispensing manifold and one or more adsorbent-based gas storagedispensing vessels mounted in the enclosure and joined in gas flowcommunication with the gas dispensing manifold, wherein eachadsorbent-based gas storage and dispensing vessel in the enclosurecomprises: a storage and dispensing vessel constructed and arranged forholding a solid-phase physical sorbent medium, and for selectivelyflowing gas into and out of said vessel; a solid-phase physical sorbentmedium disposed in said storage and dispensing vessel at an interior gaspressure; a sorbate gas physically adsorbed on said solid-phase physicalsorbent medium; the gas dispensing manifold being coupled in gas flowcommunication with the storage and dispensing vessel, and constructedand arranged to provide, exteriorly of said storage and dispensingvessel, a pressure below said interior pressure, to effect desorption ofsorbate gas from the solid-phase physical sorbent medium, and gas flowof desorbed gas through the dispensing assembly; wherein the solid-phasephysical sorbent medium is devoid of trace components selected from thegroup consisting of water, metals, and oxidic transition metal speciesin a concentration which is sufficient to decompose the sorbate gas insaid storage and dispensing vessel.
 33. A gas supply system according toclaim 32, wherein the solid-phase physical sorbent medium contains lessthan 350 parts-per-million by weight of trace components selected fromthe group consisting of water and oxidic transition metal species, basedon the weight of the physical sorbent medium.
 34. A gas supply systemaccording to claim 32, wherein the solid-phase physical sorbent mediumcontains less than 100 parts-per-million by weight of trace componentsselected from the group consisting of water and oxidic transition metalspecies, based on the weight of the physical sorbent medium.
 35. A gassupply system according to claim 32, wherein the solid-phase physicalsorbent medium contains no more than 1 part-per-million by weight oftrace components selected from the group consisting of water and oxidictransition metal species, based on the weight of the physical sorbentmedium.
 36. A gas supply system according to claim 32, wherein thesolid-phase physical sorbent medium concentration of trace componentsselected from the group consisting of water and oxidic transition metalspecies, based on the weight of the physical sorbent medium, isinsufficient to decompose more than 5% by weight of the sorbate gasafter 1 year at 25° C. and said interior pressure.
 37. A gas supplysystem according to claim 32, wherein the oxidic transition metalspecies are selected from the group consisting of oxides, sulfites andnitrates.
 38. A gas supply system according to claim 32, wherein thesorbate gas is a hydride gas.
 39. A gas supply system according to claim32, wherein the sorbate gas is selected from the group consisting ofsilane, diborane, arsine, phosphine, chlorine, BCl₃, BF₃, B₂D₆, tungstenhexafluoride, (CH₃)₃Sb, hydrogen fluoride, hydrogen chloride, hydrogeniodide, hydrogen bromide, germane, ammonia, stibine, hydrogen sulfide,hydrogen selenide, hydrogen telluride, and NF₃.
 40. A gas supply systemaccording to claim 32, wherein the sorbate gas is boron trifluoride. 41.A gas supply system according to claim 32, further comprising a heateroperatively arranged in relation to the storage and dispensing vesselfor selective heating of the solid-phase physical sorbent medium, toeffect thermally-enhanced desorption of the sorbate gas from thesolid-phase physical sorbent medium.
 42. A gas supply system accordingto claim 32, wherein the solid-phase physical sorbent medium comprises amaterial selected from the group consisting of silica, carbon, molecularsieves, alumina, macroreticulate polymers, kieselguhr, andaluminosilicates.
 43. A gas supply system according to claim 32, whereinthe solid-phase physical sorbent medium comprises a crystallinealuminosilicate composition.
 44. A gas supply system according to claim43, wherein the crystalline aluminosilicate composition has a pore sizein the range of from about 4 to about 13 Angstroms.
 45. A gas supplysystem according to claim 43, wherein the crystalline aluminosilicatecomposition comprises 5A molecular sieve.
 46. A gas supply systemaccording to claim 43, wherein the crystalline aluminosilicatecomposition comprises a binderless molecular sieve.
 47. A gas supplysystem according to claim 32, wherein the solid-phase physical sorbentmedium is present in said storage and dispensing vessel with achemisorbent material having a sorptive affinity for contaminants ofsaid sorbate gas therein.
 48. A gas supply system according to claim 47,wherein the chemisorbent material has a sorptive affinity for non-inertatmospheric gases.
 49. A gas supply system according to claim 47,wherein the chemisorbent material comprises a scavenger selected fromthe group consisting of: (A) a scavenger including a support havingassociated therewith, but not covalently bonded thereto, a compoundwhich in the presence of said contaminant provides an anion which isreactive to effect the removal of said contaminant, said compound beingselected from one or more members of the group consisting of: (i)carbanion source compounds whose corresponding protonated carbanioncompounds have a pKa value of from about 22 to about 36; and (ii) anionsource compounds formed by reaction of said carbanion source compoundswith the sorbate gas; and (B) a scavenger comprising: (i) an inertsupport having a surface area in the range of from about 50 to about1000 square meters per gram, and thermally stable up to at least about250° C.; and (ii) an active scavenging species, present on the supportat a concentration of from about 0.01 to about 1.0 moles per liter ofsupport, and formed by the deposition on the support of a Group IA metalselected from sodium, potassium, rubidium, and cesium and their mixturesand alloys and pyrolysis thereof on said support.
 50. A gas supplysystem according to claim 47, wherein the chemisorbent material isselected from the group consisting of potassium arsenide andtrityllithium.
 51. A gas supply system comprising a gas cabinet definingan enclosure including therein a gas dispensing manifold and ore or moreadsorbent-based gas storage and dispensing vessels mounted in theenclosure and joined in gas flow communication with the gas dispensingmanifold, each said adsorbent-based storage and dispensing vesselcomprising: a storage and dispensing vessel constructed and arranged forholding a solid-phase physical sorbent medium, and for selectivelyflowing gas into and out of said vessel; a solid-phase physical sorbentmedium disposed in said storage and dispensing vessel at an interior gaspressure; a sorbate gas physically adsorbed on said solid-phase physicalsorbent medium; the gas dispensing manifold being coupled in gas flowcommunication with the storage and dispensing vessel, and constructedand arranged to provide, exteriorly of said storage and dispensingvessel, a pressure below said interior pressure, to effect desorption ofsorbate gas from the solid-phase physical sorbent medium, and gas flowof desorbed gas through the dispensing assembly; wherein the solid-phasephysical sorbent medium concentration of trace components selected fromthe group consisting of water, metals, and oxidic transition metalspecies, based on the weight of the physical sorbent medium, isinsufficient to cause decomposition of the sorbate gas resulting in morethan a 5% rise in interior pressure after 1 week at 25° C. in saidstorage and dispensing vessel.
 52. A gas supply system according toclaim 51, wherein the solid-phase physical sorbent medium contains lessthan 350 parts-per-million by weight of trace components selected fromthe group consisting of water and oxidic transition metal species, basedon the weight of the physical sorbent medium.
 53. A gas supply systemaccording to claim 51, wherein the solid-phase physical sorbent mediumcontains less than 100 parts-per-million by weight of trace componentsselected from the group consisting of water and oxidic transition metalspecies, based on the weight of the physical sorbent medium.
 54. A gassupply system according to claim 51, wherein the solid-phase physicalsorbent medium contains no more than 1 part-per-million by weight oftrace components selected from the group consisting of water and oxidictransition metal species, based on the weight of the physical sorbentmedium.
 55. A gas supply system according to claim 51, wherein thesolid-phase physical sorbent medium concentration of trace componentsselected from the group consisting of water and oxidic transition metalspecies, based on the weight of the physical sorbent medium, isinsufficient to decompose more than 5% by weight of the sorbate gasafter 1 year at 25° C. and said interior pressure, in said storage anddispensing vessel.
 56. A gas supply system according to claim 51,wherein the oxidic transition metal species are selected from the groupconsisting of oxides, sulfites and nitrates.
 57. A gas supply systemaccording to claim 51, wherein the sorbate gas is a hydride gas.
 58. Agas supply system according to claim 51, wherein the sorbate gas isselected from the group consisting of silane, diborane, arsine,phosphine, chlorine, BCl₃, BF₃, B₂D₆, tungsten hexafluoride, (CH₃)₃Sb,hydrogen fluoride, hydrogen chloride, hydrogen iodide, hydrogen bromide,germane, ammonia, stibine, hydrogen sulfide, hydrogen selenide, hydrogentelluride, and NF₃.
 59. A gas supply system according to claim 51,wherein the sorbate gas is boron trifluoride.
 60. A boron trifluoridegas supply system comprising a gas cabinet defining an enclosureincluding therein a gas dispensing manifold and one or moreadsorbent-based gas storage and dispensing vessels mounted in theenclosure and joined in gas flow communication with the gas dispensingmanifold, each said adsorbent-based storage and dispensing vesselcomprising: a storage and dispensing vessel constructed and arranged forholding a solid-phase physical sorbent medium having a sorptive affinityfor boron trifluoride, and for selectively flowing boron trifluorideinto and out of said vessel; a solid-phase physical sorbent mediumhaving a sorptive affinity for boron trifluoride, disposed in saidstorage and dispensing vessel at an interior gas pressure; borontrifluoride gas, physically adsorbed on said solid-phase physicalsorbent medium; and the gas dispensing manifold coupled in gas flowcommunication with the storage and dispensing vessel, being constructedand arranged to provide, exteriorly of said storage and dispensingvessel, a pressure below said interior pressure, to effect desorption ofboron trifluoride gas from the solid-phase physical sorbent medium, andgas flow of desorbed boron trifluoride gas through the gas dispensingmanifold.
 61. An ion implantation system, comprising a reagent sourcefor reagent source material and an ion implantation apparatus coupled ingas flow communication with said reagent source, and wherein the reagentsource comprises: a gas cabinet defining an enclosure including thereina gas dispensing manifold and one or more adsorbent-based gas storageand dispensing vessels mounted in the enclosure and joined in gas flowcommunication with the gas dispensing manifold, each saidadsorbent-based storage and dispensing vessel comprising: a storage anddispensing vessel constructed and arranged for holding a solid-phasephysical sorbent medium, and for selectively flowing gas into and out ofsaid vessel; a solid-phase physical sorbent medium disposed in saidstorage and dispensing vessel at an interior gas pressure; a sorbate gasphysically adsorbed on said solid-phase physical sorbent medium; and thegas dispensing manifold being at least a part of flow circuitryinterconnecting the storage and dispensing vessel and said ionimplantation apparatus in gas flow communication with one another, saidflow circuitry being constructed and arranged to provide, exteriorly ofsaid storage and dispensing vessel, a pressure below said interiorpressure, to effect desorption of sorbate gas from the solid-phasephysical sorbent medium, and gas flow of desorbed gas through the flowcircuitry to the ion implantation apparatus; wherein the solid-phasephysical sorbent medium is devoid of trace components selected from thegroup consisting of water, metals and oxidic transition metal species ina sufficient concentration to decompose the sorbate gas in said storageand dispensing vessel.
 62. A gas supply system comprising a gas cabinetdefining an enclosure including therein a gas dispensing manifold andone or more adsorbent-based gas storage and dispensing vessels mountedin the enclosure and joined in gas flow communication with the gasdispensing manifold, with a cryopump coupled to said gas dispensingmanifold for pressurizing desorbed gas withdrawn from theadsorbent-based gas storage and dispensing vessels and discharging theresultingly pressurized gas.
 63. A gas supply system comprising a gascabinet defining an enclosure including therein a gas dispensingmanifold and one or more adsorbent-based gas storage and dispensingvessels mounted in the enclosure and joined in gas flow communicationwith the gas dispensing manifold, comprising a thermal monitoring andcontrol assembly for maintaining predetermined temperaturecharacteristics of the gas supply system.
 64. A gas supply systemaccording to claim 63, further comprising: a heater element forselective augmentive heating of the vessels and sorbent therein; asprinkler system arranged for operation for fire control in the cabinet;an exhaust heat sensor for monitoring temperature of gas exhausted fromthe cabinet; a toxic gas monitor for shut-down of the system when toxicgas is sensed; a scrubber for bulk sorption of gas leakage in thecabinet; and redundant pressure and temperature control means.
 65. Asemiconductor manufacturing facility, comprising: a gas supply systemcomprising a gas cabinet defining an enclosure including therein a gasdispensing manifold and one or more adsorbent-based gas storage anddispensing vessels mounted in the enclosure and joined in gas flowcommunication with the gas dispensing manifold; and a semiconductormanufacturing process unit arranged for use of gas from said gas supplysystem, and interconnected with the gas supply system by flow circuitryincluding said gas dispensing manifold for flow of gas from the gassupply system to the semiconductor manufacturing process unit.
 66. Asemiconductor manufacturing facility according to claim 65, wherein thesemiconductor manufacturing process unit comprises a process unitselected from the group consisting of: chemical vapor depositionreactors; ion implanters; photolithography tracks; etch chambers;diffusion chambers; and plasma generators.